BACKGROUND OF THE INVENTION
FIELD OF INVENTION
[0001] The present invention relates to benzofuranone derivatives. Furthermore, the present
invention relates to benzofuranone derivatives used to add into plastic for improving
the antioxidant ability of the polymer.
BACKGROUND ART
[0002] When plastic is produced and processed, high temperature thermal treatment is required.
During the process, the generation of free radicals and peroxides causes the fast
deterioration of the plastic and reduces its physical and mechanical properties. To
maintain the physical properties of the plastic, additives such as antioxidant which
can capture and quench the free radicals and peroxides are widely used for plastic
processing.
[0003] Antioxidants can be categorized into 3 types according to their distinct mechanisms.
The first type works by capturing and quenching carbon-centered radicals, and it is
called "carbon-centered radical antioxidant". The second type has a structure of hindered
phenol which works by capturing and quenching the carbon peroxides or the free radicals
of oxides, and it is called "primary antioxidant". The representative of the third
type is phosphate which works by capturing and quenching the peroxides, and it is
called "secondary antioxidant". Since carbon-centered radicals are generated at the
first stage during the oxidation of plastic, quenching the radical immediately will
be the most effective way to protect the desired materials.
[0004] There are a few types of carbon-centered radical antioxidants; one of them is the
compound with benzofuranone structure as shown below (formula (A)). Antioxidants with
this kind of structure were first developed by
Sandoz in 1980s (US 4,325,863,
US 4,338,244).
[0005] But only till the middle of 1990s did Ciba introduce the first commodity with benzofuranone
structure, Irganox HP-136 (as shown below, formula (B)). This antioxidant delivers
excellent effects when it combines with the primary and secondary antioxidants, especially
for polyolefin plastics. But it is not thermal stable due to its small molecule.
[0006] Unfortunately, the intermediate (as shown below, formula (C)) of the process for
producing HP-136 raised health concerns. The commodity was discontinued from the market
afterwards.
[0007] A new antioxidant with benzofuranone structure as shown in the following formula
(D) was disclosed in
US 2003/0109611. However, the use of this antioxidant is limited to engineering plastics such as
PBT and PU. There is no application data for polyolefin plastics.
[0008] The mechanism of benzofuranone antioxidants was first published by
J. Am. Chem. Soc., 2006, vol. 128, pp 16,432-16,433. The experiment demonstrated that the active hydrogen of the furan can transfer to
the sterically uncrowded position of the carbonyl group by resonance, thus such kind
of molecule can quench carbon-centered radicals effectively.
[0009] The hindered phenolic primary antioxidant is currently the largest single family
of antioxidants, and many derivatives are included. Among these derivatives, those
with COOH group are the most popular primary antioxidants to be applied for synthesizing
large molecules. Below are some examples of hindered phenolic primary antioxidants.
[0010] The combination of the primary antioxidant of hindered phenol series and a variety
of secondary antioxidants has been reported and commercialized (as the formula shown
below). Adding the single molecule which functionally combines the primary and secondary
antioxidants outperforms adding the primary or the secondary antioxidant individually.
However, no publication has revealed that carbon-centered radical antioxidant and
primary antioxidant can be combined in one molecule.
[0011] According to the disclosure of prior art, the derivatives of benzofuranone may provide
an excellent antioxidation ability to become a good thermal stability protector. If
the benzofuranone derivatives can be functionally combined with a primary antioxidant
to provide a synergistic effect in antioxidation, it will be a highly desired product
in the plastic field.
SUMMARY OF THE INVENTION
[0012] The present invention attempts to develop an antioxidant with the properties of both
carbon-centered radical antioxidant and primary antioxidant. When it is added into
plastic, the flowability and color stability of the plastic are improved.
[0013] To achieve this objective, the present invention presents a benzofuranone derivative
with antioxidant ability, which is provided with formula (I) as follow:
wherein n=0, 1, 2, or 3; R
1 and R
2 independently represent H or C1-C8 alkyl group; R
3 and R
4 independently represent H or C1-C6 alkyl group and excluding C1-C6 alkyl group simultaneously;
R
5 and R
6 independently represent H or C1-C6 alkyl group and excluding C1-C6 alkyl group simultaneously;
and R
7 is H or OH.
[0014] Furthermore, the present invention provides a method for stabilizing organic materials.
The steps of this method include adding a compound with the following formula (I)
structure:
wherein n=0, 1, 2, or 3; R
1 and R
2 independently represent H or C1-C8 alkyl group; R
3 and R
4 independently represent H or C1-C6 alkyl group and excluding C1-C6 alkyl group simultaneously;
R
5 and R
6 independently represent H or C1-C6 alkyl group and excluding C1-C6 alkyl group simultaneously;
and R
7 is H or OH.
[0015] The antioxidant of the present invention is used as an additive for organic materials.
The plastic added with the antioxidant is provided with better flowability and heat
resistance. Furthermore, it causes less discoloration under high temperature. The
present invention is especially suitable for adding into polymer materials to improve
material stability.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016]
FIG 1 is the schematic diagram of the mechanisms of various antioxidants.
FIG 2A is a NMR spectrometry of CT-500.
FIG 2B is a mass spectrometry of CT-500.
FIG 2C is an IR spectrometry of CT-500.
FIG 3A is a NMR spectrometry of CT-501.
FIG 3B is a mass spectrometry of CT-501.
FIG 3C is an IR spectrometry of CT-501.
FIG 4A is a NMR spectrometry of CT-502.
FIG 4B is a mass spectrometry of CT-502.
FIG 4C is an IR spectrometry of CT-502.
FIG 5 is the measured result of melt flow rate of the polymer added with the antioxidant
of the present invention and the control polymer without the adding of antioxidant.
FIG 6 is the measured result of the color stability test of the polymer added with
the antioxidant of the present invention and the control polymer without the adding
of antioxidant.
DETAILED DESCRIPTION OF THE PRESENT INVENTION
[0017] The benzofuranone derivative with antioxidation ability of the present invention
is provided with formula (I) as follow:
wherein n=0, 1, 2, or 3; R
1 and R
2 independently represent H or C1-C8 alkyl group; R
3 and R
4 independently represent H or C1-C6 alkyl group and excluding C1-C6 alkyl group simultaneously;
R
5 and R
6 independently represent H or C1-C6 alkyl group and excluding C1-C6 alkyl group simultaneously;
and R
7 is H or OH.
[0018] In one preferable embodiment, the R
3 is H, and R
4 is C3-C5 alkyl group.
[0019] In one preferable embodiment, the R
5 is H, and R
6 is C3-C5 alkyl group.
[0020] In a more preferable embodiment, the benzofuranone derivative is provided with formula
(II), (III) or (IV) as follow:
or
[0021] According to the rule for naming, compound (II) could be named as [4
-tert-butyl-2-(5-
tert-butyl
-2
-oxo-3H-benzofuran-3-yl)phenyl]benzoate (It is also called for short as compound (II)
or CT-500). Compound (III) could be named as [4-
tert-butyl-2-(5-
tert-butyl-2-oxo-3H-benzofuran-3-yl)phenyl]-3,5-di(
tert-butyl)-4-h ydroxy-benzoate (It is also called for short as compound (III) or CT-501).
Compound (IV) could be named as [4-
tert-butyl-2-(5-
tert-butyl-2-oxo-3H-benzofuran-3-yl)phenyl]-3-[3,5-di(
tert-butyl)-4-hydroxy-phenyl]-propanoate (It is also called for short as compound (IV)
or CT-502).
[0022] The present invention also provides a method for stabilizing organic materials. The
procedure includes adding a compound with the following formula (I) structure into
aforesaid materials:
wherein n=0, 1, 2, or 3; R
1 and R
2 independently represent H or C1-C8 alkyl group; R
3 and R
4 independently represent H or C1-C6 alkyl group and excluding C1-C6 alkyl group simultaneously;
R
5 and R
6 independently represent H or C1-C6 alkyl group and excluding C1-C6 alkyl group simultaneously;
and R
7 is H or OH.
[0023] In one preferable embodiment, the R
3 is H, and R
4 is C3-CS alkyl group.
[0024] In one preferable embodiment, the R
5 is H, and R
6 is C3-CS alkyl group.
[0025] The compound with formula (I) used for stabilizing organic materials in the present
invention could be classified as an antioxidant. When adding into the organic materials,
the quantity of the compound (I) relative to the organic materials is 0.01 %~10% by
weight.
[0026] In one preferable embodiment, the quantity of the compound (I) relative to the organic
materials is 0.1 %~2 % by weight.
[0027] In a more preferable embodiment, the compound (I) is provided with formula (II),
(III) or (IV) as follow:
or
[0028] The compound of the present invention could be added into organic materials, especially
polymer materials, to improve their thermal stability, and to prevent oxidation or
decomposition. It also provides a better flowability for processing the materials.
The suitable polymer materials include, but not limit to polyolefin, olefin copolymer,
polystyrene, polyparamethylstyrene, polymethylstyrene or the copolymer or the branched
copolymer of the same, polymer or copolymer with halogen, homopolymer or copolymer
of cyclic ethers, polyaldehyde, polyphenylene oxide, polyphenylene sulfide, polycyanurethane,
polyamide and amide copolymer, polyurea, polyimide, polyamide-imide, polycarbonate,
polyester/carbonate, unsaturated polyester resin, thermalsetting acrylate resin or
acrylate resin containing melamine resin, urea resin or polycyanate or epoxy resin
of the mixture of aforesaid various polymer.
[0029] Furthermore, the present invention could be used with any given auxiliary for organic
materials. The auxiliary may include antioxidant, UV absorber and light stabilizer,
metal deactivator, phosphate ester and phosphite ester, base-costabilizer, nucleating
agent, filler and intensifier, plasticizer, lubricant, emulsifier, surfactant, coloring
matter, optical brightener, flame retardant, antistatic additive and blowing agent,
especially antioxidant. It could be combined with the traditional phosphorous-based
antioxidant or the hindered phenol-based antioxidant to let the organic materials
with these additives equipped with a superior thermal resistance, antioxidation ability
and a better flowability for processing.
[0030] It should be easily understood that the compound of the present invention and the
use and application of the same are not limited by the different synthesis ways for
producing the compound. The exemplified examples of synthesis are used to prove the
existence of the compound of the present invention, not to limit the scope of the
present invention.
[0031] The compound of the present invention could be synthesized from the esterification
of hydroxylphenyl benzofuran-2-one and benzoic acid derivatives. The following examples
are exemplified to introduce the special aspects of the present invention, not to
limit the scope of the present invention.
Example 1: Synthesis of [4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-benzofuran-3-yl)phenyl]benzoate (CT-500)
[0032] Mix 22.5g heptane with 0.11g Methanesulfonic acid, 11.25g p-tert-butyl phenol and
5.65g glyoxylic acid and reflux for dehydrate. Filter and dry the result solution
to obtain 5-(
tert-butyl)-3-[5-(
tert-butyl)-2-hydroxyphenol]-benzofuran-2(3H)-one.
[0033] Take 33.7g (100 mmol) 5-(
tert-butyl)-3-[5-(
tert-butyl)-2-hydroxyphenol]-benzofuran-2(3H)-one, 12.81g (105 mmol) benzoic acid and
70mL toluene in a 250 mL three-necked round-bottom flask and add with 0.337g (1.8
mol) p-toluenesulfonic acid. The mixture is refluxed to remove water by Dean-Stark
apparatus for 6 hours. Cool down the mixture until the temperature goes down to 60
°C then add 5.4g (35 mmol) phosphorus oxychloride and remove the Dean-Stark apparatus
to reflux for 6 hours. The mixture is cooled down to room temperature (20 °C) and
added 50 g water for neutralization. Separate the organic layer and extract solvent
to get light yellow primary product. Mix the primary product with 100g cyclohexane
and heat to reflux for 1 hour to get the educt. Cool down the mixture solution to
room temperature (20 °C) and filter it followed with drying by hot-air oven to get
37.6g (85 mmol) white solid product with 95% yield and 99.6% purity. The identity
information of the product are shown at FIG 2a, 2b and 2c.
Example 2: Synthesis of [4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-benzofuran-3-yl)phenyl] -3,5-di(tert-butyl)-4-hydroxy-benzoate (CT-501)
[0034] Mix 22.5g heptane with 0.11g Methanesulfonic acid, 11.25g p-tert-butyl phenol and
5.65g glyoxylic acid and reflux for dehydrate. Filter and dry the result solution
to obtain 5-(
tert-butyl)-3-[5-(
tert-butyl)-2-hydroxyphenol]-benzofuran-2(3H)-one. Take 33.7g (100 mmol) 5-(
tert-butyl)-3-[5-(
tert-butyl)-2-hydroxyphenol]-benzofuran-2(3H)-one, 26.3g (105 mmol) 3,5-di(
tert-butyl)-4-hydroxy-benzoic acid and 70mL toluene in a 250 mL three-necked round-bottom
flask and add with 0.337g (1.8 mmol) p-toluenesulfonic acid. The mixture is refluxed
to remove water by Dean-Stark apparatus for 6 hours. Cool down the mixture until the
temperature down to 60 °C then add 5.4g (35 mmol) phosphorus oxychloride and remove
the Dean-Stark apparatus to reflux for 6 hours. The mixture is cooled down to room
temperature (20 °C) and added 50 g water for neutralization. Separate the organic
layer and extract solvent to get light yellow primary product. Mix the primary product
with 100 g methanol and heat to reflux for 1 hour to get the educt. Cool down the
mixture solution to room temperature (20 °C) and filter it followed with drying by
hot-air oven to get 45.6g (80 mmol) white solid product with 80% yield and 99.8% purity.
The identity information of the product are shown at FIG 3a, 3b and 3c.
Example 3: Synthesis of [4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-benzofuran-3-yl)phenyl]-3-[3,5-di(tert-butyl)-4-hydroxyphenol]-propanoate (CT-502)
[0035] Mix 22.5g heptane with 0.11g Methanesulfonic acid, 11.25g p-
tert-butyl phenol and 5.65g glyoxylic acid and reflux for dehydrate. Filter and dry the
result solution to obtain 5-(
tert-butyl)-3-[5-(
tert-butyl)-2-hydroxyphenol]-benzofuran-2(3H)-one. Take 33.7g (100 mmol) 5-(
tert-butyl)-3-[5-(
tert-butyl)-2-hydroxyphenol]-benzofuran-2(3H)-one, 29.23g (105 mmol) 3-[3,5-di(
tert-butyl)-4-hydroxy-phenyl] propanic acid, 0.337g (1.8 mol) p-toluenesulfonic and 70mL
dichloromethane in a 250 mL three-necked round-bottom flask and add with 17.84g (150
mmol) thionyl chloride . The mixture is stirred in ice bath (5°C) for 3 days. Warm
the mixture until the temperature up to room temperature (20 °C) and added 50 g water
for neutralization. Separate the organic layer and extract solvent to get light yellow
primary product. Mix the primary product with 100 g cyclohexane and heat to reflux
for 1 hour to get the educt. Filter the result solution and dry by hot-air oven to
get 35.96g (63 mmol) white solid product with 63% yield and 99.8% purity. The identity
information of the product are shown at FIG 4a, 4b and 4c.
Example 4: The applied characteristic analysis of the compounds of the present invention
[0036] To prove the stability of the compounds of the present invention, we design a formulation
which the present invention is added into the commercialized antioxidant. The melt
flow rate (MFR) and color stability (Yi) of these formulations are tested. The hydrotalcite
is used as a hydrolysis stabilizer.
[0037] Wherein, Deox 604 and Deox 10 are commodities purchased from Chitec Chemical Co.,
LTD.
Melt flow rate (MFR) testing
[0038] The MFR is obtained from polypropylene added with 0.06% by weight of the aforesaid
formulations and 0.1% by weight of calcium stearate. The ratio is listed in the following
table:
[0039] The polypropylenes are extruded once, three times and five times respectively by
twin-screw extruder (Coperion STS 35, L/D=36) under the conditions of 220°C and 40-50
rpm, followed by sampling for the MFR test. The test is based on ASTM D1238 and proceeded
under the conditions of 190°C and 2.16 kg, and the unit of the obtained data is g/10min..
The data had been collected to plot FIG 5. The Y axis coordinate is the value of MFR,
and the X axis coordinate represents the assigned numbers of the control and the experiment
formulations extruded once, three times and five times. FIG 5 indicates that groups
2, 3 and 4 added with the compound of the present invention have a smaller variation
of MFR than group 1. It shows that the compound of the present invention is contributive
for maintaining the characteristics of polymer.
Color difference test
[0040] The test relates to how compound of the present invention influences the color stability
of polymer, and it is processed by the aforesaid polypropylene formulations with once,
three times and five times extrusion. The values obtained from the colorimeter (Nippon
Denshoku, ZE2000) are collected to plot the FIG 6. The Y axis coordinate is the value
of color difference (Yi), and the X axis coordinate represents the assigned numbers
of the control and the experiment formulations extruded once, three times and five
times. Fig 6 indicates that groups 2, 3 and 4 added with the compound of the present
invention have a smaller variation of Yi than group1. It shows that the compound of
the present invention is contributive for maintaining the characteristics of polymer,
especially for improving the antioxidization ability and processing resistance of
polymer materials.
[0041] In conclusion, the benzofuranone derivatives of the present invention are provided
with a greater molecular weight, and the proportion of the carbon-centered radical
antioxidant is lower under the same weight condition. Nevertheless, the benzofuranone
derivatives provide a synergistic antioxidation capability because a primary antioxidant
portion is contained. We surprisingly discover that the compound provided by Example
2 has excellent performances in MFR test and color difference test, which proves that
the compounds of the present invention could be used as a thermal stability protector
for plastics, thus it is a new antioxidant component.
[0042] The embodiments and the technical principles used are described above. All variations
and modifications of the present invention and the uses thereof are included in the
scope of the present invention if they do not depart from the spirit of the disclosure
of this specification.
1. A benzofuranone derivative with antioxidant ability, which is provided with formula
(I) as follow:
wherein n=0, 1, 2, or 3;
R1 and R2 independently represent H or C1-C8 alkyl group;
R3 and R4 independently represent H or C1-C6 alkyl group and excluding C1-C6 alkyl group simultaneously;
R5 and R6 independently represent H or C1-C6 alkyl group and excluding C1-C6 alkyl group simultaneously;
and
R7 is H or OH.
2. The benzofuranone derivative according to claim 1, wherein R3 is H, and R4 is C3-CS alkyl group.
3. The benzofuranone derivative according to claim 1, wherein R5 is H, and R6 is C3-CS alkyl group.
4. The benzofuranone derivative according to claim 1, which is provided with formula
(II), (III) or (IV) as follow:
or
5. A method for stabilizing organic materials, including adding a compound with the following
formula (I) structure into aforesaid organic materials:
wherein n=0, 1, 2, or 3;
R1 and R2 independently represent H or C1-C8 alkyl group;
R3 and R4 independently represent H or C1-C6 alkyl group and excluding C1-C6 alkyl group simultaneously;
R5 and R6 independently represent H or C1-C6 alkyl group and excluding C1-C6 alkyl group simultaneously;
and
R7 is H or OH.
6. The method according to claim 5, wherein said compound is used as an antioxidant.
7. The method according to claim 5, wherein the quantity of said compound relative to
said organic materials is 0.01 %~10 % by weight.
8. The method according to claim 7, wherein the quantity of said compound relative to
said organic materials is 0.1 %~2 % by weight.
9. The method according to claim 5, wherein said compound is
or
10. The method according to claim 5, wherein said organic materials are polymer materials.
1. Benzofuranonderivat mit Antioxidansvermögen, das die folgende Formel (I) hat:
wobei n = 0, 1, 2 oder 3 ist;
R1 und R2 unabhängig voneinander H oder eine C1- bis C8-Alkylgruppe darstellen;
R3 und R4 unabhängig voneinander H oder eine C1- bis C6-Alkylgruppe darstellen, wobei ausgeschlossen ist, dass sie gleichzeitig eine C1- bis C6-Alkylgruppe sind;
R5 und R6 unabhängig voneinander H oder eine C1- bis C6-Alkylgruppe darstellen, wobei ausgeschlossen ist, dass sie gleichzeitig eine C1- bis C6-Alkylgruppe sind; und
R7 H oder OH ist.
2. Benzorfuranonderivat nach Anspruch 1, wobei R3 H ist und R4 eine C3- bis C5-Alkylgruppe ist.
3. Benzofuranonderivat nach Anspruch 1, wobei R5 H ist und R6 eine C3- bis C5-Alkylgruppe ist.
4. Benzofuranonderivat nach Anspruch 1, das die folgende Formel (II), (III) oder (IV)
hat:
oder
5. Verfahren zur Stabilisierung von organischen Materialien, bei dem eine Verbindung
mit der folgenden Struktur der Formel (I) zu den erwähnten organischen Materialien
gegeben wird:
wobei n = 0, 1, 2 oder 3 ist;
R1 und R2 unabhängig voneinander H oder eine C1- bis C8-Alkylgruppe darstellen;
R3 und R4 unabhängig voneinander H oder eine C1- bis C6-Alkylgruppe darstellen, wobei ausgeschlossen ist, dass sie gleichzeitig eine C1- bis C6-Alkylgruppe sind;
R5 und R6 unabhängig voneinander H oder eine C1- bis C6-Alkylgruppe darstellen, wobei ausgeschlossen ist, dass sie gleichzeitig eine C1- bis C6-Alkylgruppe sind; und
R7 H oder OH ist.
6. Verfahren nach Anspruch 5, bei dem die Verbindung als Antioxidans verwendet wird.
7. Verfahren nach Anspruch 5, bei dem die Menge der Verbindung, bezogen auf die organischen
Materialien, 0,01 Gew% bis 10 Gew% beträgt.
8. Verfahren nach Anspruch 7, bei dem die Menge der Verbindung, bezogen auf die organischen
Materialien, 0,1 Gew% bis 2 Gew% beträgt.
9. Verfahren nach Anspruch 5, bei dem die Verbindung
oder
ist.
10. Verfahren nach Anspruch 5, bei dem die organischen Materialien Polymermaterialien
sind.
1. Dérivé de benzofuranone, doté d'un pouvoir anti-oxydant et présentant la formule (I)
suivante :
dans laquelle
- l'indice n vaut 0, 1, 2 ou 3 ;
- R1 et R2 représentent chacun, indépendamment, un atome d'hydrogène ou un groupe alkyle en
C1-C8 ;
- R3 et R4 représentent chacun, indépendamment, un atome d'hydrogène ou un groupe alkyle en
C1-C6, mais ne peuvent pas représenter simultanément des groupes alkyle en C1-C6 ;
- R5 et R6 représentent chacun, indépendamment, un atome d'hydrogène ou un groupe alkyle en
C1-C6, mais ne peuvent pas représenter simultanément des groupes alkyle en C1-C6 ;
- et R7 représente un atome d'hydrogène ou un groupe hydroxyle.
2. Dérivé de benzofuranone, conforme à la revendication 1, dans lequel R3 représente un atome d'hydrogène et R4 représente un groupe alkyle en C3-C5.
3. Dérivé de benzofuranone, conforme à la revendication 1, dans lequel R5 représente un atome d'hydrogène et R6 représente un groupe alkyle en C3-C5.
4. Dérivé de benzofuranone, conforme à la revendication 1, qui présente l'une des formules
(II), (III) et (IV) suivantes :
5. Procédé permettant de stabiliser des matériaux organiques, comportant le fait d'incorporer
auxdits matériaux organiques un composé de formule (I) suivante :
dans laquelle
- l'indice n vaut 0, 1, 2 ou 3 ;
- R1 et R2 représentent chacun, indépendamment, un atome d'hydrogène ou un groupe alkyle en
C1-C8 ;
- R3 et R4 représentent chacun, indépendamment, un atome d'hydrogène ou un groupe alkyle en
C1-C6, mais ne peuvent pas représenter simultanément des groupes alkyle en C1-C6 ;
- R5 et R6 représentent chacun, indépendamment, un atome d'hydrogène ou un groupe alkyle en
C1-C6, mais ne peuvent pas représenter simultanément des groupes alkyle en C1-C6 ;
- et R7 représente un atome d'hydrogène ou un groupe hydroxyle.
6. Procédé conforme à la revendication 5, dans lequel ledit composé est utilisé en qualité
d'antioxydant.
7. Procédé conforme à la revendication 5, dans lequel la quantité dudit composé représente
de 0,01 à 10 % du poids desdits matériaux organiques.
8. Procédé conforme à la revendication 7, dans lequel la quantité dudit composé représente
de 0,1 à 2 % du poids desdits matériaux organiques.
9. Procédé conforme à la revendication 5, dans lequel ledit composé est celui de formule
10. Procédé conforme à la revendication 5, dans lequel lesdits matériaux organiques sont
des matériaux polymères.